Generally, seawater and waste water from a factory include a large amount of heavy metals and organic or inorganic contaminants and so are not good to humans. Recently, various harmful materials are generated in line with the development and the rapid growth of an industrial society and so, problems concerning an environmental contamination become intensified. Accordingly, development on a treating agent of the harmful materials is on demand.
In order to adsorb metal ions from an aqueous solution, a chelate ion-exchange resin, an activated carbon, an acryl amide polymer fiber, etc. may be used (S. Deng, R. Bai, J. P. Chen, J. Colloid and Interface Sci. 2003, 260, 265). Among the above described methods, the chelating method is mainly used for an isolation and condensing system. Particularly, chelating ligands illustrate specific adsorptivity onto heavy metals (O. Guvan, P. A. Kavakali, J. Appl. Polym. Sci. 2004, 93, 1705).
A method of manufacturing mesoporous materials using silica as a porous wall constituting material and a surfactant as a template material, has been reported by Kresge et al. for the first time (C. T. Kresge, M. E. Leonowitz, W. J. Roth, J. C. Vertuli, J. S. Beck, Nature, 1992, 359, 710). The mesoporous materials have a regular and porous structure (a cubic structure, a hexahedral structure, a worm structure), a high surface area (about 1,000 m2/g or over), and a homogeneous pore size, and so have a diverse application possibility.
Organic-inorganic hybrid mesoporous materials including inorganic silica as a porous wall along with a cross-linked organic material (trialkoxy silane including a cross-linked bonding of methane, ethane, butane, ethylene, acetylene, thiophene, bithiophene, phenyl, biphenyl and derivatives thereof) have been prepared {(a) Landskron, K.; Hatton, B. D.; Perovic D. D.; Ozin, G. A. Science 2003, 302, 266 (b) kapoor, M. P.; Inagaki, S. Bull. Chem. Soc. Jpn. 2006, 79, 1463 (c) Lu, Y.; Fan, H.; Doke, N.; Loy, D. A.; Assink, R. A.; LaVan, D. A.; Brinker, C. J. J. Am. Chem. Soc. 2000, 122, 5258 (d) C. Vercaemst, P. E. de Jongh, J. D. Meeldijk, B. Goderis, F. Verpoort, P. Van Der Voort, Chem. Commun., 2009, 4052}.
The organic-inorganic hybrid mesoporous materials have a high surface area (about 700 m2/g or over), a homogeneous pore size (about 250 nm), a regular porous structure (a cubic structure, a hexahedral structure, a worm structure), good physical properties, an advantageous modification property of the surface portion of the pores, a high adsorptivity and a chemical stability. Accordingly, the organic-inorganic hybrid mesoporous materials have a high application possibility including adsorption of macromolecules, adsorption of enzymes, adsorption of metal ions, a catalyst reaction, a sensor, a drug delivery, a preparation of nano material, etc. {(a) F. Hoffmann, M. Cornelius, J. Morell, M. Froba, Angew. Chem. Intl. Ed., 2006, 45, 3216 (b) K. H. Hossain, L. Mercier, Adv. Mater., 2002, 14, 1053 (c) Fukuoka, A.; Sakamoto, Y.; Guan, S.; Inagaki, S.; Sugimoto, N.; Fukushima, Y.; Hirahara, K.; lijima, S.; Ichikawa, M. J. Am. Chem. Soc. 2001, 123, 3373 (d) Burleigh, M. C.; Dai, S.; Hagaman, E. W.; Lin, J. S. Chem. Mater. 2001, 13, 2537; Yang, Q.; Kapoor, M. P.; Inagaki, S. J. Am. Chem. Soc. 2002, 124, 9694 (e) Yamamoto, K.; Nohara, Y.; Tatsumi, T. Chem. Lett. 2001, 648 (f) kapoor, M. P.; Bhaumik, A.; Inagaki, S.; Kuraoka, K.; Yazawa, T. J. Mater. Chem. 2002, 12, 3078 (g) Bhaumik, A.; Kapoo, M. P.; Inagaki, S. Chem. Commun. 2003, 470 (h) Ying, J. Y. C.; Mehnert, P.; Wong, M. S. Angew. Chem., Int. Ed. 1999, 38, 56 (i) Davis, M. E. Nature 2002, 417, 813}. Recently, the organic-inorganic hybrid mesoporous materials are known to have a high application possibility in adsorbing heavy metals from waste water {(a) C. Z. Huang, B. Hu, Z. C. Jiang, Spectrochim. Acta part B 2007, 62, 454 (b) S. R. Yousefi, M. Salavati-Niasari, Talanta 2009, 80, 212}.
The manufacture of the mesoporous materials including various cross-linked organic materials in the porous wall has a limitation. Generally, the mesoporous materials including the various cross-linked organic materials may be manufactured by simultaneously mixing a surfactant as a main template material and an organic-inorganic hybrid material as a porous wall forming material. In this case, though the manufacturing process may be simple, cross-linked functional organic groups may be included in the porous wall and so, the porous structure may frequently collapse. In addition, the preparation of a precursor including the various cross-linked functional groups is a difficult task. Therefore, the manufacture of the organic-inorganic hybrid mesoporous materials including various functional groups in the porous wall is difficult {(a) K. H. Hossain, L. Mercier, Adv. Mater., 2002, 14, 1053 (b) M. Kuruk, M Jaroniec, S. Guan, S. Inagaki, J. Phys. Chem. B, 2001, 105, 681 (c) M. Alvaro, B. Ferrer, V. Fornes, H. Garcia, Chem. Commun., 2001, 24, 2546 (d) G. Zhu, D. J. Jones, J. Zajac, R. Dutartre, M. Rhomari, J. Rozie, Chem. Mater., 2002, 14, 4886 (e) J. Liu, J. Yang, Q. Yang, G. Wang, Y. Li, Adv. Puna Mater., 2005, 15}.
In order to improve the above-described defect, a post-synthesis method may be applied (F. Hoffmann, M. Cornelius, J. Morell, M. Frba, Angew. Chem. Int. Ed. 2006, 45, 321). According to the method, a surfactant or a block copolymer polymer may be used as the template material and an inorganic material such as silica may be used as the porous wall forming material. Through a hydrothermal reaction under an acidic or alkaline condition, an inorganic mesoporous material may be obtained in the first step. In the second step, a reaction of a precursor including an organic group having a functionality is carried out with the surface portion of the pores to fix thereon the organic group having diverse applicability. Silanol (Si—OH) groups present at the surface portion of the pores in the organic-inorganic hybrid mesoporous silica material may be advantageously used for modifying the organic groups having various functional groups. Accordingly, the surface the pores of the mesoporous silica material may be modified using the organic groups having various functional groups and may be expected to have a selective adsorption with respect to metal ions {(a) Q. Cai, W. Y. Lin, F. S. Xiao, W. Q. Pang, X. H. Chen, B. S. Zuo, Micropor. Mesopor. Mater, 1999, 32, 1 (b) B. J. S. Johnson, A. Stein, Inorg. Chem. 2001, 40, 801 (c) M. R. Ganjali, A. Daftari, L. Hagiagha-Babaci, Water, Air, Soil Pollut, 2006, 173, 71}.
Considering the above, the inventors of the present application has been suggested a silica precursor including a functional group having a cross-linked 2,6-diamino pyridine group.
FIG. 26 illustrates a chemical scheme reported by the present inventors in a society of The 3rd Asian Symposium on Advanced Materials' (Sep. 19, 2011˜Sep. 22, 2011).
The silica precursor including a functional group having a cross-linked 2,6-diamino pyridine group may be used as an organic-inorganic hybrid porous wall forming material, and a block copolymer may be used as a template material. Through a hydrothermal reaction, an organic-inorganic hybrid mesoporous silica material may be synthesized and through a post synthesis method using chlorosulfonic acid, an organic-inorganic hybrid mesoporous silica material including a sulfonic acid group in the porous wall may be formed.
However, referring to FIG. 26, in order to obtain the organic-inorganic silica precursor using 2,6-diamino pyridine and 3-isocyanatopropyl triethoxysilane as reacting materials, a refluxing at a temperature of about 85° C. and an atmosphere of an inert gas (N2) may be required to implement a reaction. In addition, the reaction using 3-isocyanato triethoxysilane may require to be performed in a glove box. Further, a side reaction may be readily occurred during performing the synthetic method of the organic-inorganic hybrid silica precursor.
Among ten rare metals (lithium, cobalt, molybdenum, manganese, tungsten, titanium, magnesium, indium, a rare-earth metal, chrome) drawing attention by the government as a part of securing resources, cobalt is mostly coated on an anode of a secondary battery to be used as a main component of an anode material to impart functions of storing and supplying exterior energy. Cobalt is an important rare metal drawing attention as a necessary and strategy metal in the present primary core industry. Considering the circumstances of lacking in the natural resources, the separation and condensation of cobalt as a high value product is very important. Recently, an international price of cobalt is rapidly increasing and a confirmation of the core materials including cobalt is necessary.
The separation and condensation of cobalt has been performed using a metal oxide such as TiO2 as an adsorbing agent {(a) Param H Tewari, Woon Lee, J Colloid Interface, 1975, 52, 77 (b) Jae Chun Ryu, Hyun Soo Yang, Yu Hwan Kim, Ki Woung Sung, Yong lk Kim, J IND ENG CHEM, 1996, 7, 1192 (c) Hiroki Tamuraa, Noriaki Katayamab, Ryusaburo Furuichia, J Colloid Interface, 1997, 195, 192}. However, the structure of the metal oxide may collapse and so the efficiency of the adsorbing agent may decrease (S. J. Hwang, J. Korean Chem. Soc, 2004, 48, 46).
Bhattacharyya et al. performed an experiment on cobalt adsorption using an inorganic oxide, montmorillonite (Krishna G. Bhattacharyya, Susmita Sen Gupta, Applied Clay Science, 2008, 41, 1-9). However, the adsorption selectivity was not found in a specific artificial solution.
As described above, the metal oxide as the conventional adsorbing agent for performing a selective cobalt adsorption is weak to an environment such as a strong acid, and an inorganic oxide has no adsorption selectivity in a specific artificial solution.